JP6690934B2 - Underwater photorefractive display and manufacturing method thereof - Google Patents
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Images
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- Toys (AREA)
- Laminated Bodies (AREA)
Description
本発明は水中用光屈折表示体及びその製造方法に関する。更に詳細には、空気中と水中で表示部が異なる様相を示す水中用光屈折表示体及びその製造方法に関する。 The present invention relates to an underwater photorefractive display and a method for manufacturing the same. More specifically, the present invention relates to an underwater photorefractive display body in which the display portion is different in air and water and a manufacturing method thereof.
従来、支持体上に疎水性シリカをバインダー樹脂に分散状態に固着させた吸液状態と非吸液状態で透明性が異なる多孔質層を設けた変色性積層体が開示されている(例えば、特許文献1参照)。
前記変色性積層体は、水が付着しても変色することなく、特定界面張力値未満の液体が多孔質層に付着すると吸液により透明化し、下層の色や像を視認することができるものであって、天候、使用場所に左右されず、水以外の液体で変色させる用途や、水では変色しないことを目的とする用途に適用される。
これとは別に、空気中で視認される様相と、水中で視認される様相が異なり、変化性を付与する試みとして、絵を描いた紙を透明袋に入れて水中に浸漬すると描いた絵が見えなくなる水中マジックカードが開示されている(例えば、非特許文献1参照)。
前記水中マジックカードは、絵が空気中では袋内の空気と透明袋を介して視認されるが、水中に浸漬すると透明袋と水の屈折率が近いため、絵が視認されなくなる。
前記水中マジックカードは、空気中で視認される絵が水中で視認されなくなるといった面白さを付与できるものの、絵を透明袋に入れる手間を要したり、袋に水が入ると変化しなくなるといった不具合を生じることがあった。
Conventionally, there has been disclosed a color-changing laminate in which a porous layer having different transparency in a liquid-absorption state and a non-liquid-absorption state in which hydrophobic silica is fixed to a binder resin in a dispersed state is provided on a support (for example, See Patent Document 1).
The discolorable laminate does not discolor even when water adheres, and when a liquid having a specific interfacial tension value adheres to the porous layer, it becomes transparent due to liquid absorption, and the color and image of the lower layer can be visually recognized. In addition, the present invention is applied to applications in which a color other than water is used for discoloration, and applications where it is not discolored in water, regardless of the weather and place of use.
Apart from this, the appearance seen in the air and the appearance seen in water are different, and as an attempt to add variability, the picture drawn is put in a transparent bag and immersed in water. An invisible underwater magic card is disclosed (for example, see Non-Patent Document 1).
In the underwater magic card, the picture is visually recognized in the air through the air inside the bag and the transparent bag, but when immersed in water, the picture becomes invisible because the transparent bag and the water have a close refractive index.
Although the underwater magic card can add fun such that the picture visible in the air is not visible in the water, it takes trouble to put the picture in a transparent bag and it does not change when water enters the bag Could occur.
本発明は、簡便に空気中と水中で表示部が異なる様相を示す水中用光屈折表示体及びその製造方法を提供しようとするものである。 SUMMARY OF THE INVENTION The present invention is intended to provide an underwater photorefractive display body and a method for manufacturing the same, in which the display portion in air and water is different.
本発明は、支持体表面に、疎水性シリカを有機溶剤可溶性樹脂に分散状態に固着させた撥水性表示部を設けてなり、前記疎水性シリカと有機溶剤可溶性樹脂との質量比率が1:2〜1:5であり、撥水性表示部の界面張力値が0mN/m以上、50mN/m未満であり、且つ、前記支持体と撥水性表示部の間に、疎水性シリカを有機溶剤可溶性樹脂に分散状態に固着させた撥水性補強層を設け、前記撥水性補強層に含まれる疎水性シリカの含有率が撥水性表示部に含まれる疎水性シリカの含有率よりも3%以上低い水中用光屈折表示体を要件とする。
更には、支持体表面に、疎水性シリカと、有機溶剤と、有機溶剤可溶性樹脂とからなる液状物を印刷又は塗装し、有機溶剤を除去して撥水性補強層を設け、前記撥水性補強層上に、疎水性シリカと、有機溶剤と、有機溶剤可溶性樹脂とからなる液状物を印刷又は塗装し、有機溶剤を除去して撥水性表示部を設ける水中用光屈折表示体の製造方法を要件とする。
In the present invention, a water-repellent display portion is provided on a surface of a support, wherein hydrophobic silica is fixed to an organic solvent-soluble resin in a dispersed state, and the mass ratio of the hydrophobic silica and the organic solvent-soluble resin is 1: 2. to 1: 5, the interfacial tension value of the water repellent display is 0 mN / m or more, 50 mN / m less than der is, and, between the support and the water repellent display unit, an organic solvent-soluble hydrophobic silica A water-repellent reinforcing layer fixed to a resin in a dispersed state is provided, and the content of the hydrophobic silica contained in the water-repellent reinforcing layer is 3% or more lower than the content of the hydrophobic silica contained in the water-repellent display part. A photorefractive display is required.
Furthermore, the supporting bearing member surface, and hydrophobic silica, and an organic solvent, a liquid composed of an organic solvent-soluble resin was printed or painted, the water-repellent reinforcing layer provided by removing the organic solvent, the water-repellent reinforcing A method for producing an underwater photorefractive display element, in which a hydrophobic silica, an organic solvent, and a liquid material composed of an organic solvent-soluble resin are printed or coated on the layer to remove the organic solvent and provide a water-repellent display part, As a requirement.
本発明は、簡便に空気中と水中で表示部が異なる様相を視認可能な水中用光屈折表示体及びその製造方法を提供できる。 INDUSTRIAL APPLICABILITY The present invention can provide an underwater photorefractive display body and a method for manufacturing the same, in which it is possible to easily visually recognize different display portions in air and water.
本発明の水中用光屈折表示体は、支持体表面に、疎水性シリカを有機溶剤可溶性樹脂に分散状態に固着させた撥水表示部を設けてなる。
前記支持体の材質は特に限定されるものではなく、紙、合成紙、編物、織物、不織布等の布帛、合成皮革、レザー、プラスチック、金属、ガラス、陶磁器、木材、石材等が挙げられる。
前記支持体の形状は特に限定されるものではなく、平面形状、シート状の他、曲面や凹凸を有する形状であってもよい。
なお、前記支持体と撥水表示部の間に着色剤を含む着色層を設けることもできる。
The underwater photorefractive indicator of the present invention is provided with a water repellent indicator in which hydrophobic silica is fixed in a dispersed state in an organic solvent-soluble resin on the surface of a support.
The material of the support is not particularly limited, and examples thereof include paper, synthetic paper, knit, woven fabric, non-woven fabric, synthetic leather, leather, plastic, metal, glass, ceramics, wood, stone and the like.
The shape of the support is not particularly limited, and may be a plane shape, a sheet shape, or a shape having a curved surface or unevenness.
A colored layer containing a colorant may be provided between the support and the water repellent display portion.
次に、撥水性表示部に含まれる疎水性シリカについて説明する。
シリカは製造方法により乾式法と湿式法に分類されるが、いずれも表面にはシラノール基が配列された構造である。
疎水性シリカはシラノール基にメチルクロロシラン等のシラン、ポリジメチルシロキサン等のシロキサン、ヘキサメチルジシラザン等を反応させて、シラノール基のもつ親水性を疎水性に変えるため、水を吸収できないのみならず撥水性を示す。
汎用の疎水性シリカとしては、東ソー・シリカ株式会社製の商品名Nipsil SS−10、同SS−20、同SS−70、同SS−40、同SS−50、同SS−100、日本アエロジル株式会社製の商品名AEROSIL R972、同RY50、R812、同R805、同RX200、同RY200、キャボットカーボン社製の商品名TS−530、同TS−610、同TS−720、デグサジャパン株式会社製の商品名AEROSIL R202,同R805、同R812、株式会社トクヤマ製の商品名REOLOSIL MT−10、同DM−10、同DM−20S、富士シリシア化学株式会社製の商品名SYLOPHOBIC100、同200、同704、同4004、同507、同702、同505、同603等が挙げられる。
前記疎水性シリカは、屈折率が1.4〜1.8の範囲にある。
前記疎水性シリカの粒子径は特に限定されるものではないが、0.03〜10.0μmのものが好適に用いられる。粒子径測定にはレーザー回折/光散乱式粒子径分布測定装置(堀場製作所製LA−300)又は動的光散乱式粒子径分布測定装置(堀場製作所製SZ−100)により測定する。
又、前記疎水性シリカは2種以上を併用することもできる。
Next, the hydrophobic silica contained in the water repellent display portion will be described.
Silica is classified into a dry method and a wet method depending on the manufacturing method, and both have a structure in which silanol groups are arranged on the surface.
Hydrophobic silica reacts silanol groups with silanes such as methylchlorosilane, siloxanes such as polydimethylsiloxane, and hexamethyldisilazane to change the hydrophilicity of silanol groups to hydrophobic, so that it cannot absorb water. Shows water repellency.
As the general-purpose hydrophobic silica, trade name Nipsil SS-10, SS-20, SS-70, SS-40, SS-50, SS-100, Nippon Aerosil Co., Ltd., manufactured by Tosoh Silica Co., Ltd. Company name AEROSIL R972, RY50, R812, R805, RX200, RY200, Cabot Carbon Co., Ltd. product names TS-530, TS-610, TS-720, Degussa Japan Co., Ltd. products Name AEROSIL R202, same R805, same R812, trade name REOLOSIL MT-10, same DM-10, same DM-20S made by Tokuyama Corporation, product name SYLOPHOBIC100, same 200, same 704, same made by Fuji Silysia Chemical Ltd. 4004, 507, 702, 505, 603 and the like.
The hydrophobic silica has a refractive index in the range of 1.4 to 1.8.
The particle size of the hydrophobic silica is not particularly limited, but a particle size of 0.03 to 10.0 μm is preferably used. For the particle size measurement, a laser diffraction / light scattering type particle size distribution measuring device (LA-300 manufactured by Horiba Ltd.) or a dynamic light scattering type particle size distribution measuring device (SZ-100 manufactured by Horiba Ltd.) is used.
The hydrophobic silica may be used in combination of two or more kinds.
前記疎水性シリカは、有機溶剤可溶性樹脂を含む溶剤中に分散して、塗料や印刷インキ等の液状物を調製し、スクリーン印刷、オフセット印刷、グラビヤ印刷、コーター、タンポ印刷、転写等の印刷方法、刷毛塗り、スプレー塗装、静電塗装、電着塗装、流し塗り、ローラー塗り、浸漬塗装等の方法により、支持体表面に撥水性表示部を設ける。
前記疎水性シリカは、水分散は勿論、水系エマルジョンへの分散も通常の方法では困難であるため、有機溶剤に分散して用いる。
前記有機溶剤可溶性樹脂は有機溶剤に溶解又は分散してなり、疎水性シリカを含む液状組成物を支持体上に全体又は部分的に塗工、乾燥して水中用光屈折表示体が得られる。
前記有機溶剤可溶性樹脂とは、30℃で有機溶剤に対して5重量%以上溶解する樹脂である。
The hydrophobic silica is dispersed in a solvent containing an organic solvent-soluble resin to prepare a liquid material such as a paint or a printing ink, and a printing method such as screen printing, offset printing, gravure printing, coater, tampo printing, and transfer. The water repellent display portion is provided on the surface of the support by a method such as brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, roller coating and dip coating.
Since it is difficult to disperse the hydrophobic silica in a water-based emulsion as well as in an aqueous emulsion by an ordinary method, the hydrophobic silica is used by being dispersed in an organic solvent.
The organic solvent-soluble resin is dissolved or dispersed in an organic solvent, and a liquid composition containing hydrophobic silica is coated on a support in whole or in part and dried to obtain an underwater photorefractive display.
The organic solvent-soluble resin is a resin that dissolves at 5% by weight or more in an organic solvent at 30 ° C.
前記有機溶剤としては、n−パラフィン系溶剤、イソパラフィン系溶剤、ナフテン系溶剤、芳香族系溶剤、α−オレフィン系溶剤等の石油系溶剤、軽油、スピンドル油、マシン油、シリンダー油、テレピン油、ミネラルスピリット、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、酢酸エチル、酢酸プロピル、酢酸ブチル、乳酸エチル、キシレン、トルエン、エタノール、イソプロピルアルコール、ブタノール等が挙げられる。 Examples of the organic solvent include n-paraffin solvents, isoparaffin solvents, naphthene solvents, aromatic solvents, petroleum solvents such as α-olefin solvents, light oil, spindle oil, machine oil, cylinder oil, turpentine oil, Mineral spirits, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, propyl acetate, butyl acetate, ethyl lactate, xylene, toluene, ethanol, isopropyl alcohol, butanol and the like can be mentioned.
前記有機溶剤可溶性樹脂としては、ウレタン系樹脂、アクリル酸エステル樹脂、アクリル酸エステル共重合樹脂、アクリルポリオール樹脂、塩化ビニル−酢酸ビニル共重合樹脂、マレイン酸樹脂、ポリエステル樹脂、スチレン樹脂、スチレン共重合樹脂、ポリカーボネート樹脂、エポキシ樹脂、スチレン−ブタジエン共重合樹脂、アクリロニトリル−ブタジエン共重合樹脂、メタクリル酸メチル−ブタジエン共重合樹脂、ブタジエン樹脂、クロロプレン樹脂、メラミン樹脂、カゼイン、澱粉、ポリビニルアルコール、尿素樹脂、フェノール樹脂等、アクリル系樹脂、ポリエステル系樹脂、アルキッド系樹脂、スチレン系樹脂、ナイロン系樹脂、酢酸ビニル系樹脂、塩化ビニル系樹脂、アクリロニトリル−ブタジエン−スチレン共重合樹脂、セルロース系樹脂等が挙げられる。
前記疎水性シリカと有機溶剤可溶性樹脂の混合比率は、疎水性シリカの種類及び性状に左右されるが、好ましくは、疎水性シリカ1質量部に対して樹脂固形分2〜5質量部であり、より好ましくは、2〜3.5質量部である。疎水性シリカ1質量部に対して樹脂固形分が2質量部未満の場合には、形成される撥水性表示部の実用的な皮膜強度を得ることが困難であり、5質量部を越える場合には、前記疎水性シリカが撥水性表示部表面に配向する量が少なくなり、水中での光屈折効果を発現し難くなる。
前記撥水性表示部は、一般的な塗膜と比較して疎水性シリカに対する有機溶剤可溶性樹脂の混合比率が小さいため、十分な皮膜強度が得られ難い。そこで、前記の有機溶剤可溶性樹脂のうち、ナイロン系樹脂、ウレタン系樹脂、アクリル系樹脂を用いて耐擦過強度を高めることが好ましい。
前記ウレタン系樹脂としては、ポリエステル系ウレタン樹脂、ポリカーボネート系ウレタン樹脂、ポリエーテル系ウレタン樹脂等があり、2種以上を併用することもできる。
前記ウレタン系樹脂は単独で用いることもできるが、支持体の種類や皮膜に必要とされる性能に応じて、他のバインダー樹脂を併用することもできる。
前記有機溶剤可溶性樹脂において、架橋性のものは任意の架橋剤を添加して架橋させることにより、さらに皮膜強度を向上させることができる。
前記有機溶剤可溶性樹脂は乾燥被膜が疎水性を示す樹脂と、親水性を示す樹脂があり、好ましくは乾燥被膜が疎水性となる樹脂を用いると水中での光屈折効果が大きくなる。
また、有機溶剤可溶性樹脂は乾燥後の皮膜に撥水性を持たせるため、フッ素樹脂やシリコーン樹脂を単独或いは併用して用いることが好ましく、前記樹脂を用いることにより疎水性シリカの添加量が比較的少なくても水中での光反射効果を発現できる。
前記撥水性表部中には着色剤を含有させることもできる。
Examples of the organic solvent-soluble resin include urethane resins, acrylic ester resins, acrylic ester copolymer resins, acrylic polyol resins, vinyl chloride-vinyl acetate copolymer resins, maleic acid resins, polyester resins, styrene resins, styrene copolymers. Resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, casein, starch, polyvinyl alcohol, urea resin, Phenolic resin, acrylic resin, polyester resin, alkyd resin, styrene resin, nylon resin, vinyl acetate resin, vinyl chloride resin, acrylonitrile-butadiene-styrene copolymer resin, Loin resins.
The mixing ratio of the hydrophobic silica and the organic solvent-soluble resin depends on the type and properties of the hydrophobic silica, but is preferably 2 to 5 parts by mass of resin solid content relative to 1 part by mass of the hydrophobic silica, More preferably, it is 2 to 3.5 parts by mass. When the resin solid content is less than 2 parts by mass with respect to 1 part by mass of the hydrophobic silica, it is difficult to obtain a practical film strength of the water-repellent display part formed, and when it exceeds 5 parts by mass. Reduces the amount of the hydrophobic silica oriented on the surface of the water-repellent display portion, and makes it difficult to exhibit the photorefractive effect in water.
In the water-repellent display part, since the mixing ratio of the organic solvent-soluble resin to the hydrophobic silica is small as compared with a general coating film, it is difficult to obtain sufficient film strength. Therefore, it is preferable to increase the scratch resistance by using a nylon resin, a urethane resin, or an acrylic resin among the organic solvent-soluble resins.
Examples of the urethane-based resin include polyester-based urethane resin, polycarbonate-based urethane resin, and polyether-based urethane resin, and two or more kinds of them can be used in combination.
The urethane-based resin may be used alone, or may be used in combination with another binder resin depending on the type of the support and the performance required for the film.
In the organic solvent-soluble resin, a crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent to effect crosslinking.
The organic solvent-soluble resin includes a resin having a dry dry film and a resin having a hydrophilic dry film. Preferably, when a resin having a dry dry film is used, the photorefractive effect in water becomes large.
Further, since the organic solvent-soluble resin imparts water repellency to the film after drying, it is preferable to use a fluororesin or a silicone resin alone or in combination. By using the resin, the addition amount of the hydrophobic silica is relatively small. At least a light reflection effect in water can be exhibited.
A colorant may be contained in the water repellent surface portion.
前記水中用光屈折表示体の撥水性表示部は界面張力値が0mN/mを超え、且つ、以上50mN/m未満である。
前記界面張力値が50mN/m以上の場合、水への親和性が高くなり水中光屈折効果が発現し難くなる。
The water-repellent display portion of the underwater photorefractive display element has an interfacial tension value of more than 0 mN / m and more than 50 mN / m.
When the interfacial tension value is 50 mN / m or more, the affinity for water becomes high and the underwater photorefractive effect becomes difficult to be exhibited.
前記のようにして得られる水中用光屈折表示体は、水に浸漬すると疎水性シリカの細孔中の空気により撥水性表示部表面と水との間に空気層が形成され、水と空気との屈折率の差から見る角度により水と空気層との界面で光の屈折が発生し、鏡のように反射する現象を生じて空気中とは異なる様相(空気中では視認されなかった銀色の反射光)が視認される。本発明の要点は疎水性シリカを撥水表示部表面に配設することである。 The underwater photorefractive display element obtained as described above, when immersed in water, an air layer is formed between the water and the water repellent display surface due to the air in the pores of the hydrophobic silica, Depending on the angle of view from the difference in the refractive index of light, light refraction occurs at the interface between the water and the air layer, causing a phenomenon that reflects like a mirror, causing a different appearance from that in air (a silver color that was not visible in air. The reflected light is visible. The point of the present invention is to dispose hydrophobic silica on the surface of the water repellent display portion.
更に、前記支持体と撥水性表示部の間に、疎水性シリカを有機溶剤可溶性樹脂に分散状態に固着させた撥水性補強層を設け、撥水性補強層に含まれる疎水性シリカの含有率は、撥水性表示部に含まれる疎水性シリカの含有率よりも3%以上低くすることにより、撥水性表示部にひび割れを生じることを防止できる。
支持体上に撥水性表示部を直接設けるとひび割れを生じ易い。これは、疎水性シリカと、有機溶剤可溶性樹脂と、有機溶剤からなる撥水性表示部用インキを支持体に塗装又は印刷等の方法で塗工して形成される撥水性表示部は、乾燥時に表示部内での対流及び有機溶剤が蒸発することによる粘度特性としてのチクソ性が大きくなって流動し難くなり、対流と平滑性を保てないまま乾燥しようとする双方の現象から撥水表示部にひび割れを生じ易くなると考えられる。
前記ひび割れの改良を検討したところ、支持体と撥水性表示部との間に撥水性表示部と同じ疎水性シリカを含む撥水性補強層を設け、撥水性補強層に含まれる疎水性シリカの含有率を撥水性表示部に含まれる疎水性シリカの含有率よりも3%以上低くすることによって、前述の支持体に撥水性表示部を設ける系と比較してひび割れを起こし難くなる。
Further, between the support and the water-repellent display portion, a water-repellent reinforcing layer having hydrophobic silica fixed to an organic solvent-soluble resin in a dispersed state is provided, and the content of the hydrophobic silica contained in the water-repellent reinforcing layer is By lowering the content of the hydrophobic silica contained in the water repellent display portion by 3% or more, it is possible to prevent the water repellent display portion from cracking.
If the water-repellent display portion is directly provided on the support, cracking is likely to occur. This is because the water-repellent display part formed by applying a water-repellent display part ink comprising a hydrophobic silica, an organic solvent-soluble resin and an organic solvent on a support by a method such as painting or printing Due to convection in the display part and thixotropy as a viscosity characteristic due to evaporation of the organic solvent, it becomes difficult to flow and it becomes a water repellent display part from both phenomena of convection and attempting to dry without maintaining smoothness. It is considered that cracking is likely to occur.
Upon studying the improvement of the cracks, a water-repellent reinforcing layer containing the same hydrophobic silica as that of the water-repellent display portion was provided between the support and the water-repellent display portion, and the hydrophobic silica contained in the water-repellent reinforcement layer was contained. By making the
前記水中用光屈折表示体は、支持体表面に、疎水性シリカと、有機溶剤と、有機溶剤可溶性樹脂とからなる液状物を印刷又は塗装し、有機溶剤を除去して撥水性表示部を設ける製造方法、或いは、支持体表面に、疎水性シリカと、有機溶剤と、有機溶剤可溶性樹脂とからなる液状物を印刷又は塗装し、有機溶剤を除去して撥水性補強層を設け、前記撥水性補強層上に、疎水性シリカと、有機溶剤と、有機溶剤可溶性樹脂とからなる液状物を印刷又は塗装し、有機溶剤を除去して撥水性表示部を設ける製造方法により得ることができる。 The underwater photorefractive indicator is provided with a water-repellent indicator by printing or coating a liquid material composed of hydrophobic silica, an organic solvent, and an organic solvent-soluble resin on the surface of the support and removing the organic solvent. A method for production, or by printing or coating a liquid material comprising hydrophobic silica, an organic solvent, and an organic solvent-soluble resin on the surface of the support, removing the organic solvent to provide a water repellent reinforcing layer, It can be obtained by a manufacturing method in which a liquid material composed of hydrophobic silica, an organic solvent, and an organic solvent-soluble resin is printed or coated on the reinforcing layer, and the organic solvent is removed to provide the water repellent display portion.
前記水中用光屈折表示体は、水中玩具、船や潜水艦を模した玩具、水中ゲーム用品、水中装飾用品、釣りの疑似餌、潜水等の水中作業用表示体、観賞魚用水槽加飾用具、水着等に用いられる。
前記水中装飾用品としては、曲面を有するプラスチック成形体に撥水性表示部を設けた水中用光屈折表示体を可動部に取り付け、水中で可動部を作動させることにより、水中用光屈折表示体が作動し、見る角度を変えることなく撥水性表示部が光の屈折により視認されなくなり、銀色の反射光が視認される装飾用品が挙げられる。
前記可動部としては、モーターやエアポンプが挙げられ、モーターを用いて水中用光屈折表示体を回転させたり、エアポンプを用いて空気により水中用光屈折表示体を動かす構成が挙げられる。
The underwater photorefractive display is an underwater toy, a toy imitating a ship or a submarine, an underwater game product, an underwater decoration product, a pseudo bait for fishing, a display for underwater work such as diving, an ornamental fish tank decoration tool, Used for swimwear.
As the underwater decorative article, the underwater photorefractive display body is obtained by attaching an underwater photorefractive display body having a water repellent display section to a plastic molded body having a curved surface to the movable section and operating the movable section in water. An example is a decorative article that is activated and the water-repellent display part becomes invisible due to refraction of light without changing the viewing angle, and the silver reflected light is visually recognized.
Examples of the movable portion include a motor and an air pump. Examples of the movable portion include a configuration in which the underwater photorefractive display body is rotated by using a motor, and the underwater photorefractive display body is moved by air using an air pump.
以下に実施例を記載するが、本発明はこれら実施例に限定されない。
なお、実施例中の部は質量部である。
界面張力値の測定方法
撥水性表示部表面の界面張力はJIS K6768ぬれ張力試験方法に従い測定した。
疎水性シリカの屈折率測定方法
(株)島津製作所製接触液(屈折液)を使用し、液浸法(ベッケ線法)にて測定した。
Examples will be described below, but the present invention is not limited to these examples.
The parts in the examples are parts by mass.
Method for measuring interfacial tension value The interfacial tension on the surface of the water-repellent display part was measured according to the JIS K6768 wet tension test method.
Method for measuring refractive index of hydrophobic silica It was measured by a liquid immersion method (Becke line method) using a contact liquid (refractive liquid) manufactured by Shimadzu Corporation.
参考例1(図1参照)
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS20〕9.8部、有機溶剤可溶性樹脂として塩化ビニル−酢酸ビニル共重合樹脂(日信化学工業(株)製、製品名ソルバインC 固形分100%)20部、シクロヘキサノン50部、ノニオン系添加剤1部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:2.04)。
支持体2として100μm厚の青色キャストコート紙上に、前記撥水性表示部用インキを用いて、スクリーン印刷により円形の撥水性表示部3を設けて水中用光屈折表示体1を得た。
前記撥水性表示部表面の界面張力は45mN/mであった。
前記水中用光屈折表示体は、空気中では青色基材上に淡青色の円形の撥水性表示部が視認され、見る角度を変えても円形の撥水性表示部は常に視認された。
前記水中用光屈折表示体を水中に浸漬し、見る角度を変えると視認されていた円形の撥水性表示部は光の屈折により視認されなくなり、銀色の反射光が視認された。
前記水中用光屈折表示体を水中から取り出すと円形の撥水性表示部は常に視認され、前記様相変化は繰り返し行うことができた。
Reference example 1 (see Figure 1)
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS20] 9.8 parts, vinyl chloride-vinyl acetate copolymer resin as organic solvent-soluble resin (Nisshin Chemical Industry Co., Ltd., product name Solvain C solid (100%), 20 parts of cyclohexanone, 50 parts of cyclohexanone, and 1 part of a nonionic additive were mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.04).
A circular water-
The interfacial tension on the surface of the water repellent display part was 45 mN / m.
In the underwater photorefractive display body, a light blue circular water-repellent display portion was visually recognized on the blue base material in the air, and the circular water-repellent display portion was always visually recognized even when the viewing angle was changed.
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the circular water-repellent display portion which had been visually recognized became invisible due to the refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive display was taken out of water, the circular water-repellent display was always visible, and the appearance change could be repeated.
参考例2
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕2部、赤色顔料(クラリアント(株)製、製品名HOSTAPERM RED D3G)0.05部、有機溶剤可溶性樹脂として溶剤型フッ素系樹脂(DIC(株)製、製品名ディフェンサTR−101 固形分31%)10部、シクロヘキサノン2部、イソシアネート系硬化剤(DIC(株)製、製品名バーノックDN−950 固形分75%)2部、ノニオン系添加剤1部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:2.3)。
支持体として100μm厚の透明ポリエチレンテレフタレートフィルム上に、前記撥水性表示部用インキを用いて、スクリーン印刷により縞模様の撥水表示部を設けて水中用光屈折表示体を得た
前記撥水性表示部表面の界面張力は39mN/mであった。
前記水中用光屈折表示体は、空気中では透明な支持体上に淡赤色の縞模様の撥水性表示部が視認され、見る角度を変えても縞模様の撥水性表示部は常に視認された。
前記水中用光屈折表示体を水中に浸漬し、見る角度を変えると視認されていた縞模様の撥水性表示部は光の屈折により視認されなくなり、銀色の反射光が視認された。
前記水中用光屈折表示体を水中から取り出すと縞模様の撥水性表示部は常に視認され、前記様相変化は繰り返し行うことができた。
Reference example 2
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 2 parts, red pigment (Clariant Co., Ltd., product name HOSTAPERM RED D3G) 0.05 part, solvent type fluorine resin as organic solvent soluble resin (DIC Corporation, product name Defencer TR-101 solid content 31%) 10 parts,
A water-repellent display was obtained by providing a striped water-repellent display by screen printing using a water-repellent display ink on a 100 μm thick transparent polyethylene terephthalate film as a support. The interfacial tension on the surface of the part was 39 mN / m.
In the underwater photorefractive display member, a light red striped water repellent display portion was visually recognized on a transparent support in the air, and the striped water repellent display portion was always visually recognized even when the viewing angle was changed. .
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the striped water-repellent display portion which had been visually recognized disappeared due to the refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of the water, the striped water-repellent display was always visible, and the appearance change could be repeated.
参考例3
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕2.3部、青色顔料(クラリアント(株)製、製品名HOSTAPERM BLUE B2G)0.05部、有機溶剤可溶性樹脂として溶剤型アクリル樹脂〔DIC(株)製、製品名アクリディックA−801−P 固形分50%〕10部、酢酸ブチル20部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:2.2)。
支持体として白色ABS板上に、前記撥水性表示部用インキを用いて、スプレー塗装によりハート形の撥水性表示部を設けて水中用光屈折表示体を得た。
前記撥水性表示部表面の界面張力は39mN/mであった。
前記水中用光屈折表示体は、空気中では透明な支持体上に淡青色のハート形の撥水性表示部が視認され、見る角度を変えてもハート形の撥水性表示部は常に視認された。
前記水中用光屈折表示体を水中に浸漬し、見る角度を変えると視認されていたハート形の撥水性表示部は光の屈折により視認されなくなり、銀色の反射光が視認された。
前記水中用光屈折表示体を水中から取り出すとハート形の撥水性表示部は常に視認され、前記様相変化は繰り返し行うことができた。
Reference example 3
2.3 parts of hydrophobic silica [manufactured by Tosoh Silica Co., Ltd., product name Nipseal SS50A], 0.05 part of blue pigment (Clariant Co., Ltd., product name HOSTAPERM BLUE B2G), solvent-type acrylic as an organic solvent-soluble resin An ink for a water-repellent display part was obtained by mixing 10 parts of a resin [manufactured by DIC Corporation, product name: Acridic A-801-P solid content 50%] and 20 parts of butyl acetate (hydrophobic silica and organic solvent soluble). Resin solids ratio, 1: 2.2).
A water-repellent display for water was obtained by providing a heart-shaped water-repellent display by spray coating using a water-repellent display ink on a white ABS plate as a support.
The interfacial tension on the surface of the water repellent display part was 39 mN / m.
In the underwater photorefractive display body, a light blue heart-shaped water-repellent display portion was visually recognized on a transparent support in the air, and the heart-shaped water-repellent display portion was always visually recognized even when the viewing angle was changed. .
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the heart-shaped water-repellent display portion, which had been visually recognized, became invisible due to refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of water, the heart-shaped water-repellent indicator was always visible, and the appearance change could be repeated.
撥水性表示部用インキAの調製
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕2部、青色顔料〔クラリアント(株)製、製品名HOSTAPERM BLUE B2G〕0.05部、有機溶剤可溶性樹脂として溶剤型フッ素系樹脂〔DIC(株)製、製品名ディフェンサTR−101 固形分31%〕20部、酢酸ブチル20部、イソシアネート系硬化剤〔旭化成(株)製、製品名デュラネート24A−100 固形分100%〕1.7部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:4.0)。
撥水性表示部用インキBの調製
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕2.3部、青色顔料〔クラリアント(株)製、製品名HOSTAPERM BLUE B2G〕0.07部、溶剤型フッ素系樹脂〔DIC(株)製、製品名ディフェンサTR−101 固形分31%〕20部、酢酸ブチル20部、イソシアネート系硬化剤〔旭化成(株)製、製品名デュラネート24A−100 固形分100%〕1.7部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:3.4)。
撥水性表示部用インキCの調製
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕2.7部、青色顔料〔クラリアント(株)製、製品名HOSTAPERM BLUE B2G〕0.08部、有機溶剤可溶性樹脂として溶剤型フッ素系樹脂〔DIC(株)製、製品名ディフェンサTR−101 固形分31%〕20部、酢酸ブチル20部、イソシアネート系硬化剤〔旭化成(株)製、製品名デュラネート24A−100 固形分100%〕1.7部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:2.9)。
撥水性表示部用インキDの調製
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕3.3部、青色顔料〔クラリアント(株)製、製品名HOSTAPERM BLUE B2G〕0.1部、有機溶剤可溶性樹脂として溶剤型フッ素系樹脂〔DIC(株)製、製品名ディフェンサTR−101 固形分31%〕20部、酢酸ブチル20部、イソシアネート系硬化剤〔旭化成(株)製、製品名デュラネート24A−100 固形分100%〕)1.7部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:2.4)。
Preparation of ink A for water-
Preparation of ink B for water-repellent display part 2.3 parts of hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A], blue pigment [Clariant Co., product name HOSTAPERM BLUE B2G] 0.07 part , Solvent type fluorine resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, butyl acetate 20 parts, isocyanate type curing agent [Asahi Kasei Co., Ltd., product name Duranate 24A-100 solid Min. 100%] 1.7 parts was mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 3.4).
Preparation of ink C for water-repellent display part Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 2.7 parts, Blue pigment [Clariant Co., product name HOSTAPERM BLUE B2G] 0.08 part , An organic solvent-soluble resin, a solvent-type fluororesin [manufactured by DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, butyl acetate 20 parts, an isocyanate curing agent [manufactured by Asahi Kasei Co., Ltd., product name Duranate 24A-100 solid content 100%] 1.7 parts was mixed to obtain an ink for water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.9).
Preparation of Ink D for Water-Repellent Display Part Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 3.3 parts, Blue pigment [Clariant Co., product name HOSTAPERM BLUE B2G] 0.1 part , An organic solvent-soluble resin, a solvent-type fluororesin [manufactured by DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, butyl acetate 20 parts, an isocyanate curing agent [manufactured by Asahi Kasei Co., Ltd., product name Duranate 24A-100 solid content 100%]) was mixed to obtain an ink for a water-repellent display portion (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.4).
水中用光屈折表示体の作製
支持体として白色ABS板上に、前記撥水性表示部用インキA乃至Dを用いて以下の表に示される構成にてスプレー塗装して参考例4乃至9及び実施例1乃至4の水中用光屈折表示体を得た。
参考例8及び実施例1乃至4における撥水性表示部用インキA及びBは、撥水性補強層として設けられる。
参考例9は、白色ABS板上にアクリル樹脂50%酢酸ブチル溶液10部、酢酸ブチル20部を混合したクリヤーインキを塗装した後、撥水性表示部用インキDを塗装して撥水性表示部を設けて水中用光屈折表示体を得た。
Production of Underwater Photorefractive Display A white ABS plate as a support was spray-coated with the inks A to D for the water-repellent display in the constitutions shown in the following Tables and Reference Examples 4 to 9 and Examples. The underwater photorefractive indicators of Examples 1 to 4 were obtained.
The water-repellent display portion inks A and B in Reference Example 8 and Examples 1 to 4 are provided as water-repellent reinforcing layers.
In Reference Example 9 , a white ABS plate was coated with a clear ink prepared by mixing 10 parts of a 50% butyl acetate solution of acrylic resin and 20 parts of butyl acetate, and then an ink D for a water-repellent display part was applied to the water-repellent display part. The photorefractive indicator for underwater was obtained by providing.
表中の各検討項目の評価内容は次の通りである。
水中光屈折試験
作製した水中光屈折体を空気中で角度を変えて観察し、反射面(鏡面)が見えるかを確認する。
次に、水中光屈折体を水中に浸漬して空気中と同じように角度を変えて観察し、反射面(鏡面)が見えるかを確認する。
◎:良好な光屈折性を示して反射面(鏡面)が視認される。
○:光屈折性を示して反射面(鏡面)が視認される。
●:やや光屈折性が低いものの、実用性を満たす反射面(鏡面)が視認される。
外観(ひび割れ)試験
水中用光屈折表示体の外観(撥水性表示部)のひび割れの有無を確認した。
◎:外観のひび割れは見られない。
○:外観に僅かなひび割れが見られるものの、実用性を満たしている。
●:外観にひび割れが見られるものの、実用性を満たしている。
接着性試験
水中光屈折体の撥水性表示部に粘着テープを荷重500gで貼着し、60°の角度で剥がして撥水性表示部(塗膜)の剥離を確認する。
◎:撥水性表示部の剥離は見られなかった。
○:撥水性表示部に剥離は見られるものの、実用性を満たしている。
The evaluation contents of each examination item in the table are as follows.
Underwater photorefraction test Observe the fabricated underwater photorefractive body in the air at different angles to see if the reflecting surface (mirror surface) is visible.
Next, the underwater light refracting body is immersed in water and the angle is changed in the same manner as in the air to observe, and it is confirmed whether the reflecting surface (mirror surface) can be seen.
⊚: Good photorefractive property is shown, and the reflection surface (mirror surface) is visually recognized.
◯: Shows light refractivity and the reflection surface (mirror surface) is visually recognized.
●: A reflective surface (mirror surface) that has practicality is visually recognized although the optical refraction is slightly low.
Appearance (Crack) Test The presence or absence of cracks in the appearance (water repellent display part) of the underwater photorefractive indicator was confirmed.
⊚: No external cracks are found.
◯: Practicality is satisfied although there are slight cracks in the appearance.
●: The appearance is cracked, but it is practical.
Adhesion Test An adhesive tape is attached to the water-repellent display part of the underwater light refracting body under a load of 500 g, and peeled off at an angle of 60 ° to confirm the peeling of the water-repellent display part (coating film).
A: No peeling of the water-repellent display part was observed.
◯: Peeling is observed in the water-repellent display part, but the practicality is satisfied.
参考例10
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕9部、有機溶剤可溶性樹脂としてアクリル樹脂(DIC(株)製、製品名アクリディックA−166 固形分45%)40部、シクロヘキサノン20部、ノニオン系添加剤1部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:2.0)。
支持体として青色ポリエステルサテン生地上に、前記撥水性表示部用インキを用いてスクリーン印刷により星形を印刷し、120℃で加温して有機溶剤を除去して撥水性表示部を設けて水中用光屈折表示体を得た。
前記撥水性表示部表面の界面張力は40mN/mであった。
前記水中用光屈折表示体は、空気中では青色基材上に淡青色の星形の撥水性表示部が視認され、見る角度を変えても星形の撥水性表示部は常に視認された。
前記水中用光屈折表示体を水中に浸漬し、見る角度を変えると視認されていた星形の撥水性表示部は光の屈折により視認されなくなり、銀色の反射光が視認された。
前記水中用光屈折表示体を水中から取り出すと星形の撥水性表示部は常に視認され、前記様相変化は繰り返し行うことができた。
Reference example 10
Nine parts of hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A], 40 parts of an acrylic resin (DIC Co., Ltd., product name Acridic A-166 solid content 45%) as an organic solvent-soluble resin, cyclohexanone 20 parts and 1 part of a nonionic additive were mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 2.0).
On a blue polyester satin fabric as a support, a star shape is printed by screen printing using the ink for the water-repellent display portion, heated at 120 ° C. to remove the organic solvent, and the water-repellent display portion is provided to provide a water-repellent display portion. A photorefractive display was obtained.
The interfacial tension on the surface of the water repellent display part was 40 mN / m.
In the underwater photorefractive display element, a light blue star-shaped water-repellent display portion was visually recognized on a blue base material in the air, and the star-shaped water-repellent display portion was always visually recognized even when the viewing angle was changed.
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the star-shaped water-repellent display portion that had been visually recognized disappeared due to refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of water, the star-shaped water-repellent indicator was always visible, and the appearance change could be repeated.
参考例11
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS20〕5部、疎水性シリカ〔フジシリシア化学(株)製、製品名SYLOPHOBIC100〕5部、有機溶剤可溶性樹脂として塩化ビニル−酢酸ビニル共重合樹脂(日信化学工業(株)製、製品名ソルバインC 固形分100%)20部、シクロヘキサノン20部、酢酸ブチル5部、ノニオン系添加剤1部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:2)。
支持体として半球形状の赤色ABS樹脂上に、前記撥水性表示部用インキを用いて、タンポ印刷により「P」の文字の印刷を行い、室温で1日放置して有機溶剤を蒸発させて、撥水性表示部を設けて水中用光屈折表示体を得た。
前記撥水性表示部表面の界面張力は45mN/mであった。
前記水中用光屈折表示体は、空気中では赤色基材上に淡赤色の「P」文字の撥水性表示部が視認され、見る角度を変えても「P」文字の撥水性表示部は常に視認された。
前記水中用光屈折表示体を水中に浸漬し、見る角度を変えると視認されていた「P」文字の撥水性表示部は光の屈折により視認されなくなり、銀色の反射光が視認された。
前記水中用光屈折表示体を水中から取り出すと「P」文字の撥水性表示部は常に視認され、前記様相変化は繰り返し行うことができた。
Reference example 11
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS20] 5 parts, hydrophobic silica [Fuji Silysia Chemical Co., Ltd., product name SYLOPHOBIC100] 5 parts, vinyl chloride-vinyl acetate copolymer as organic solvent soluble resin 20 parts of resin (manufactured by Nissin Chemical Industry Co., Ltd., product name Solvain C solid content 100%), 20 parts of cyclohexanone, 5 parts of butyl acetate and 1 part of nonionic additive are mixed to obtain an ink for a water-repellent display part. (Hydrophobic silica and organic solvent soluble resin solid ratio, 1: 2).
On the hemispherical red ABS resin as a support, the letter "P" was printed by tampo printing using the water-repellent display ink and left at room temperature for 1 day to evaporate the organic solvent, A water repellent display portion was provided to obtain an underwater photorefractive display member.
The interfacial tension on the surface of the water repellent display part was 45 mN / m.
In the underwater photorefractive display body, the water-repellent display portion of the light red "P" character is visually recognized on the red base material in the air, and the water-repellent display portion of the "P" character is always visible even if the viewing angle is changed. Was seen.
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the water repellent display portion of the "P" character that had been visually recognized became invisible due to the refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of the water, the water repellent display portion of the letter "P" was always visible, and the appearance change could be repeated.
実施例5(図2参照)
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕2.3部、青色顔料〔クラリアント(株)製、製品名HOSTAPERM BLUE B2G〕0.07部、溶剤型フッ素系樹脂〔DIC(株)製、製品名ディフェンサTR−101 固形分31%〕20部、シクロヘキサノン10部、イソシアネート系硬化剤〔旭化成(株)製、製品名デュラネート24A−100 固形分100%〕1.7部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:3.4)。
支持体2としてピンク色塩化ビニルシートに、前記撥水性表示部用インキを用いてスクリーン印刷にてハート型の印刷を行い、その後60℃で加温を行い、有機溶剤を蒸発させて撥水性補強層4を設けた。
次に、疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕2部、青色顔料〔クラリアント(株)製、製品名HOSTAPERM BLUE B2G〕0.05部、有機溶剤可溶性樹脂として溶剤型フッ素系樹脂〔DIC(株)製、製品名ディフェンサTR−101 固形分31%〕20部、シクロヘキサノン10部、イソシアネート系硬化剤〔旭化成(株)製、製品名デュラネート24A−100 固形分100%〕1.7部、ノニオン系添加剤1部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:4.0)。
前記撥水性表示部用インキを用いて、前記撥水性補強層上にスクリーン印刷にて同じ大きさ、形状にハート型の印刷を行い、その後60℃で加温乾燥して、撥水性表示部3を設けて水中用光屈折表示体1を得た。
前記撥水性表示部表面の界面張力は39mN/mであった。
前記水中用光屈折表示体は、空気中ではピンク色基材上に淡紫色のハート型の撥水性表示部が視認され、見る角度を変えてもハート型の撥水性表示部は常に視認された。
前記水中用光屈折表示体を水中に浸漬し、見る角度を変えると視認されていたハート型の撥水性表示部は光の屈折により視認されなくなり、銀色の反射光が視認された。
前記水中用光屈折表示体を水中から取り出すとハート型の撥水性表示部は常に視認され、前記様相変化は繰り返し行うことができた。
Example 5 (see FIG. 2)
2.3 parts of hydrophobic silica [manufactured by Tosoh Silica Co., Ltd., product name Nipseal SS50A], 0.07 part of blue pigment [manufactured by Clariant Co., Ltd., product name HOSTAPERM BLUE B2G], solvent type fluorine resin [DIC ( Co., Ltd., product name Defencer TR-101 solid content 31%] 20 parts, cyclohexanone 10 parts, isocyanate curing agent [Asahi Kasei Co., Ltd. product name Duranate 24A-100 solid content 100%] 1.7 parts are mixed. Thus, an ink for a water-repellent display portion was obtained (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 3.4).
Heart-shaped printing is performed on the pink vinyl chloride sheet as the
Next, hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 2 parts, blue pigment [Clariant Co., Ltd., product name HOSTAPERM BLUE B2G] 0.05 part, solvent type as an organic solvent soluble resin Fluorine-based resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 20 parts, cyclohexanone 10 parts, isocyanate-based curing agent [Asahi Kasei Corporation, product name Duranate 24A-100 solid content 100%] 1.7 parts and 1 part of a nonionic additive were mixed to obtain an ink for a water-repellent display part (solid ratio of hydrophobic silica and organic solvent-soluble resin, 1: 4.0).
Using the ink for the water-repellent display portion, heart-shaped printing is performed on the water-repellent reinforcing layer in the same size and shape by screen printing, and then heated and dried at 60 ° C. to obtain the water-
The interfacial tension on the surface of the water repellent display part was 39 mN / m.
In the underwater photorefractive display body, a light purple heart-shaped water-repellent display portion was visually recognized on a pink substrate in the air, and the heart-shaped water-repellent display portion was always visually recognized even when the viewing angle was changed. .
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the heart-shaped water-repellent display portion, which had been visually recognized, became invisible due to refraction of light, and silver-colored reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of the water, the heart-shaped water-repellent indicator was always visible, and the appearance change could be repeated.
参考例12
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕9部、青色顔料〔クラリアント(株)製、製品名HOSTAPERM BLUE B2G〕0.1部、有機溶剤可溶性樹脂としてアクリル樹脂(DIC(株)製、製品名アクリディックA−166 固形分45%)40部、酢酸エチル40部、ノニオン系添加剤1部を混合して撥水性表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:2.0)。
支持体として透明ポリエステルフィルム上に、前記撥水性表示部用インキを用いて、グラビア印刷により水玉柄を印刷し、100℃で加温して有機溶剤を除去して、撥水性表示部を設けて水中用光屈折表示体を得た。
前記撥水性表示部表面の界面張力は40mN/mであった。
前記水中用光屈折表示体は、空気中では透明基材上に淡青色の水玉柄の撥水性表示部が視認され、見る角度を変えても水玉柄の撥水性表示部は常に視認された。
前記水中用光屈折表示体を水中に浸漬し、見る角度を変えると視認されていた水玉柄の撥水性表示部は光の屈折により視認されなくなり、銀色の反射光が視認された。
前記水中用光屈折表示体を水中から取り出すと水玉柄の撥水性表示部は常に視認され、前記様相変化は繰り返し行うことができた。
Reference example 12
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 9 parts, blue pigment [Clariant Co., Ltd., product name HOSTAPERM BLUE B2G] 0.1 part, acrylic resin (DIC ( Co., Ltd., product name Acridic A-166 (solid content 45%) 40 parts, ethyl acetate 40 parts, and nonionic additive 1 part were mixed to obtain a water-repellent display ink (hydrophobic silica and organic solvent). Soluble resin solids ratio, 1: 2.0).
A polka dot pattern was printed by gravure printing on the transparent polyester film as a support using the ink for water-repellent display, and the organic solvent was removed by heating at 100 ° C. to provide a water-repellent display. An underwater photorefractive display was obtained.
The interfacial tension on the surface of the water repellent display part was 40 mN / m.
In the underwater photorefractive indicator, a light blue water-repellent display portion of a polka dot pattern was visually recognized on a transparent substrate in the air, and a water-repellent display portion of a polka dot pattern was always visually recognized even when the viewing angle was changed.
When the underwater photorefractive indicator was immersed in water and the viewing angle was changed, the water-repellent display portion with a polka dot pattern that had been visually recognized became invisible due to refraction of light, and silver reflected light was visually recognized.
When the underwater photorefractive indicator was taken out of the water, the water-repellent indicator of the polka dot pattern was always visible, and the appearance change could be repeated.
比較例1
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕0.5部、赤色顔料〔クラリアント(株)製、製品名HOSTAPERM RED D3G〕0.01部、有機溶剤可溶性樹脂として溶剤型フッ素系樹脂〔DIC(株)製、製品名ディフェンサTR−101 固形分31%〕10部、シクロヘキサノン2部、イソシアネート系硬化剤〔DIC(株)製、製品名バーノックDN−950 固形分75%〕2部、ノニオン系添加剤1部を混合して表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形比率、1:9.2)。
支持体として100μm厚の透明ポリエチレンテレフタレートフィルム上に、前記表示部用インキを用いてスクリーン印刷により縞模様の表示部を設けて表示体を得た。
前記表示部表面の界面張力は45mN/mであった。
前記表示体は、空気中では透明な支持体上に淡赤色の縞模様の表示部が視認され、見る角度を変えても縞模様の撥水性表示部は常に視認された。
前記表示体を水中に浸漬し、見る角度を変えても縞模様の表示部は常に視認され、光の屈折により視認されなくなる現象を生じなかった。
Comparative Example 1
0.5 parts of hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A], 0.01 part of red pigment [Clariant Co., Ltd., product name HOSTAPERM RED D3G], solvent type fluorine as an organic solvent-soluble resin System resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 10 parts,
A transparent polyethylene terephthalate film having a thickness of 100 μm was used as a support, and a striped display portion was provided by screen printing using the above-described ink for the display portion to obtain a display member.
The interfacial tension on the surface of the display part was 45 mN / m.
In the display body, the light red striped display portion was visually recognized on the transparent support in the air, and the striped water repellent display portion was always visually recognized even when the viewing angle was changed.
Even when the display body was dipped in water and the viewing angle was changed, the striped display portion was always visually recognized, and the phenomenon that the display portion was not visually recognized due to refraction of light did not occur.
比較例2
疎水性シリカ〔東ソー・シリカ(株)製、製品名ニップシールSS50A〕4部、赤色顔料〔クラリアント(株)製、製品名HOSTAPERM RED D3G〕0.1部、有機溶剤可溶性樹脂として溶剤型フッ素系樹脂〔DIC(株)製、製品名ディフェンサTR−101 固形分31%〕10部、シクロヘキサノン2部、イソシアネート系硬化剤〔DIC(株)製、製品名バーノックDN−950 固形分75%〕2部、ノニオン系添加剤1部を混合して表示部用インキを得た(疎水性シリカと有機溶剤可溶性樹脂の固形分比率、1:1.2)。
支持体として100μm厚の透明ポリエチレンテレフタレートフィルム上に、前記表示体用インキを用いてスクリーン印刷により縞模様の表示部を設けて表示体を得た。
前記表示部表面の界面張力は35mN/mであった。
前記表示体は、空気中では透明な支持体上に淡赤色の縞模様の表示部が視認され、見る角度を変えても縞模様の撥水性表示部は常に視認された。
前記水中用光屈折表示体を水中に浸漬し、見る角度を変えると視認されていた縞模様の撥水性表示部は光の屈折により視認されなくなり、銀色の反射光が視認された。
前記水中用光屈折表示体を水中から取り出すと縞模様の撥水性表示部は常に視認されるものの、前記接着性試験を行ったところ粘着テープで表示部が容易に剥離して繰り返しの使用を満足させることはできなかった。
Comparative example 2
Hydrophobic silica [Tosoh Silica Co., Ltd., product name Nipseal SS50A] 4 parts, red pigment [Clariant Co., Ltd., product name HOSTAPERM RED D3G] 0.1 part, solvent type fluorine resin as organic solvent soluble resin [DIC Corporation, product name Defencer TR-101 solid content 31%] 10 parts,
A 100 μm thick transparent polyethylene terephthalate film was used as a support, and a striped display portion was provided by screen printing using the above-described ink for a display to obtain a display.
The interfacial tension on the surface of the display part was 35 mN / m.
In the display body, the light red striped display portion was visually recognized on the transparent support in the air, and the striped water repellent display portion was always visually recognized even when the viewing angle was changed.
When the underwater photorefractive display body was immersed in water and the viewing angle was changed, the striped water-repellent display portion which had been visually recognized disappeared due to the refraction of light, and silver-colored reflected light was visually recognized.
Although the striped water-repellent display is always visible when the underwater photorefractive display is taken out from water, the adhesive test shows that the display can be easily peeled off with the adhesive tape to satisfy repeated use. I couldn't let you do it.
1 水中用光屈折表示体
2 支持体
3 撥水性表示部
4 撥水性補強層
1
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